CN103813869A - Feeder and shapeable composition for production thereof - Google Patents
Feeder and shapeable composition for production thereof Download PDFInfo
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- CN103813869A CN103813869A CN201280045885.6A CN201280045885A CN103813869A CN 103813869 A CN103813869 A CN 103813869A CN 201280045885 A CN201280045885 A CN 201280045885A CN 103813869 A CN103813869 A CN 103813869A
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- rice husk
- husk ash
- weight
- silica
- composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/08—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for decreasing shrinkage of the mould, e.g. for investment casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/10—Burned or pyrolised refuse
- C04B18/101—Burned rice husks or other burned vegetable material
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Silicon Compounds (AREA)
- Mold Materials And Core Materials (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Feeders are described for use in the foundry industry comprising (a) rice husk ash containing, based on the total amount of the components detectable in the rice husk ash by quantitative phase analysis using X-ray diffractometry (i) crystalline modifications of silicon dioxide, (ii) monoclinic feldspar, and (iii) amorphous silicon dioxide, a total fraction of at least 70% by weight, preferably greater than 75% by weight, of (i) crystalline modifications of silicon dioxide, and (ii) monoclinic feldspar, wherein, based on the total mass of the shapeable composition of the feeder, the amount of this rice husk ash is in the range from 5 to 50% by weight, preferably 5 to 25% by weight, (b) cured binder, (c) optionally fibrous material, (d) optionally one or more further fillers, and (e) optionally an oxidizable metal and an oxidizing agent for the oxidizable metal.
Description
Technical field
The present invention relates to for the manufacture of the application of the light filler of the composition that can be shaped of the rising head for foundry industry, the composition that can be shaped accordingly and its manufacture and for the rising head of foundry industry.At this, term " rising head " not only comprises rising head barrel, rising head insert and emits lid also to comprise heating cushion in scope herein.
Background technology
In the time manufacturing the drip molding of the metal in foundry industry, liquid metal is filled in mold and at this place and solidifies.Dwindling of process of setting and metal volume links together; And therefore conventionally in mold or use rising head thereon, to compensate volume disappearance and then prevent that the shrinkage cavity in foundry goods from forming in the time of casting solidification.Rising head is connected with foundry goods or adventurous casting region and is usually located on a side of mould cavity and/or in a side of die space.
About the hitherto known composition for the manufacture of the rising head for foundry industry, distinguish two main groups:
A. adiabatic material, that is to say, for the manufacture of the rising head barrel of thermal insulation or mat insulation or adiabatic bag can be shaped with hardenable composition (material).(sclerosis) adiabatic material first roughly absorbs and comes from the heat of liquid metal during the casting of mould, until there is equalized temperature; Light thermal break matter from this time protects liquid cast metal to prevent further thermal losses within the regular hour.The rising head being shaped by adiabatic material or adiabatic bag therefore retarded coagulation start and promote the tight feed of foundry goods.Adiabatic material generally includes filler and the adhesive of at least one graininess (granular).
B. the riser heating material of heat release, that is to say, can be that be shaped and composition hardenable heat release (material), described can be that be shaped with composition hardenable heat release by aluminothermy or similarly reaction spontaneous heating during the casting of mould.Manufacture rising head by the riser heating material (being also referred to as the moulding material of heat release) of heat release, described rising head can be encased in mould and can be to produce heat in the mode contacting with melt.Heat output is carried out according to the conversion reaction aluminothermy in pyrogen or similar at this.The heat discharging in exception in the situation that for adding the liquid metal of hot riser, in any case but all for the loss of (partly) heat compensation.In the time that use has the rising head of pyrogen of heat release, it is liquid that metal keeps more for a long time compared with rising head based on adiabatic material (A seeing above).Therefore can improve the intensive feed of foundry goods and use if desired less rising head, to such an extent as to reducing circulation share and improve casting yield.But the riser heating material of heat release is significantly more expensive than adiabatic material.The riser heating material of heat release generally include the filler, adhesive of at least one graininess (granular), relatively high share oxidation metal and for example, for the oxidant (nitrate of potassium or sodium) of the metal that can be oxidized.The preferably inexpensive metal of metal that can be oxidized.The metal that preferably, can be oxidized is selected from aluminium, magnesium, calcium and silicon.
The rising head of known a kind of thermal insulation from DE102005025771, described rising head comprises having the 0.3g/cm of being less than
3bulk density glass hollow ball, pottery hollow ball, sclerosis adhesive and comprise if desired fibrous material.The hollow ball of pottery with respect to the part by weight of glass hollow ball at this in scope at 1:1 to 10:1, preferably in the scope of 2:1 to 6:1, and the total amount of glass hollow ball and ceramic hollow ball in the gross mass of rising head in the scope of 40 % by weight to 80 % by weight, preferably in the scope of 40 % by weight to 60 % by weight.
If desired, the material that comprises other according to the rising head of DE102005025771, described other material can be called filler.For example in the time using nano combined adhesive, the existence of biological silicic acid is favourable, biological silicic acid (the product title according to DE102005025771 with Refratechnik Casting limited company of for example rice husk ash shape
(current product name becomes Nermat AF) obtains).
Rice husk ash exceed 90 % by weight, the part of conventionally to 92 % by weight to 97 % by weight is made up of silica (silicic acid).The rice husk ash of Nermat AF type take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as being less than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 70 % by weight, and (iii) amorphous silica accounts in the total amount of the husk ash composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction to be 30 % by weight or more, conventionally even to exceed 40 % by weight.The carbon content of the rice husk ash of Nermat AF type is until 1.5 % by weight.In the gross mass of the composition for the manufacture of adiabatic rising head that can be shaped, the amount of these rice husk ashes is until 15 % by weight and conventionally between 3 % by weight and 5 % by weight.
DE19728368C1 discloses a kind of heat-insulating material being made up of fine powdered acidity or alkaline adiabatic agent for cast steel, and described adiabatic agent is combined into granular materials in the matrix of formed material.As acid adiabatic agent (coverture), rice husk ash is disclosed.According to DE19728368C1, the major part of silicic acid in rice husk ash exists with unbodied form, but silica share that can be between 5% and 30% when husk in burning is also converted into crystal form.
DE19731653C2 discloses a kind of globule for the manufacture of being made up of rice husk ash or the method for bead, and described rice husk ash uses as heat-barrier material.According to DE19731653C2, husk leaves ash in the time of burning, and described ash is mainly made up of the silica of amorphous form.
US4,555,448A1 discloses a kind of material for thermal insulation, the particle that described material comprises the biogenic silica in amorphous body, preferably rice husk ash.
Summary of the invention
The hollow ball that is suitable for using in rising head can not be unrestrictedly for.Therefore the object of the invention is, propose a kind of light filler, and a kind of corresponding rising head is provided, described light filler can be shaped for the manufacture of the composition of rising head in can be used as at present mainly at least part of substitute of the hollow ball of use.By hollow ball is substituted, neither should make the impaired intensity of rising head that also should not make of insulation effect of rising head impaired.Therefore light filler should meet following major requirement:
-also in the temperature higher than 1400 ℃, the preferably heat endurance in the temperature higher than 1500 ℃; Even-in the temperature higher than 1400 ℃, the preferably enough mechanical stabilities in the temperature higher than 1500 ℃;
-low dust adheres to or does not exist dust to adhere to;
-lower than the bulk density of 800g/l;
-in the time of 100 ℃ lower than the thermal conductivity of 0.15W/mK and 1000 ℃ time lower than the thermal conductivity of 0.5W/mK.
In the scope of presents, when described particle or material neither melt in the temperature lower than given, also softening in the situation that spatial modelling loses or while decomposing, particle or material are counted as durable (stable).
Light filler not only should be suitable for adiabatic rising head but also be suitable for the rising head of heat release thus.
The invention still further relates to a kind of rising head for using at foundry industry, for the manufacture of the composition that can be shaped of rising head and for the manufacture of the method for the composition for the manufacture of rising head that can be shaped.
The object proposing according to the present invention by realizing with rice husk ash, compared with the light material of the composition that can be shaped of the rising head for the manufacture of for foundry industry, the composition of described rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, and described object realizes by a kind of rising head, described rising head comprises (a) rice husk ash, the composition of described rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, wherein in the gross mass of the composition of the shaping of rising head, the amount of described rice husk ash is in the scope of 5 % by weight to 50 % by weight, preferably in the scope of 5 % by weight to 25 % by weight, (b) adhesive of sclerosis, (c) selectable fibrous material, (d) one or more other filler and (e) metal (for example aluminium, magnesium or silicon) that selectable (in the case of the rising head of heat release) can be oxidized and the oxidant for the metal that can be oxidized if desired.
Rice husk ash (a) used according to the invention is also referred to as the rice husk ash of highly crystalline hereinafter, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight.
From document DE19728368C1, DE19731653C2 and US4, rice husk ash known in 555,448A1 is not the rice husk ash of highly crystalline with regard to restriction above, because they mainly comprise the silica of amorphous form.The rice husk ash that corresponding content is applicable to use according to DE102005025771.That is to say from DE102005025771 and cannot learn, the rice husk ash that used is herein different from the rice husk ash that the common technique of burning by husk is manufactured, wherein as from document DE19728368C1, DE19731653C2 and US4,555, known in 448A1, produce a kind of rice husk ash, described rice husk ash mainly comprises the silica of amorphous form.
Feldspar is to have ternary system K
2oAl
2o
36SiO
2-Na
2oAl
2o
36SiO
2-CaOAl
2o
32SiO
2the alumina silicate of interior component.
Rice husk ash comprises the silica between 92 % by weight and 97 % by weight conventionally, and remaining relevant composition is oxide and carbon and the water (as moisture and as the crystallization water) of sodium, potassium, calcium, magnesium, aluminium and iron.In the rice husk ash (a) of the highly crystalline using in rising head according to the present invention, the composition that preferably can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, (ii) monoclinic feldspar and the (iii) share more than 75 % by weight of amorphous silica, by the silica of (i) brilliant change modification and (ii) feldspar formation, and the share that (iii) amorphous silica accounts in the total amount of the husk ash composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction is less than 25 % by weight, especially be preferably less than 20 % by weight or be even less than 15 % by weight.The share that the form with crystalline substance change modification of the silica comprising in the rice husk ash (a) of highly crystalline exists (i) comprises the share of one or more brilliant silica that become modifications that come from the group being made up of christobalite, squama diamond stone, quartz.If desired, the rice husk ash of highly crystalline (a) also comprises (ii) monoclinic feldspar.
X-ray diffraction polycrystalline or unbodied material is also described in DIN EN13925-1 standard for the application of nondestructive test.X-ray diffraction (XRPD-X-Ray Powder Diffraction) is a kind of undamaged method of inspection (ZfP), and this allows, and determines type and the amount of the phase comprising in sample." phase " (with regard to " crystalline phase " or " thermodynamics phase ") is interpreted as to a division part common molecule or intermolecular structure of physics system, and irrelevant with the another kind segmentation that is not in relation to size distribution or shape.If sample to be analyzed is by the mixture of two or more known phase compositions (described phase is for example determined in the result of the radioactive ray identification of phases), wherein said at least one in is mutually crystallization, can determine so each crystalline phase and volume content unbodied share or mass content.The assessment of quantitative facies analysis based on the integrated intensity of one or more diffracted rays is carried out, wherein being similar to peak height as integrated intensity definite in the situation that.
In rising head according to the present invention, the determined carbon content of x-ray fluorescence analysis of passing through of rice husk ash (a) to be used is less than 1 % by weight, is preferably less than 0.1 % by weight.
Preferably there is the granularity in the scope of 0.2mm to 2mm according to the rice husk ash of highly crystalline to be used of the present invention (a), especially preferably the granularity in the scope of 0.2mm to 1.5mm.Have and expect that the part of granularity obtains by screening.Do not carry out grinding or the efflorescence of rice husk ash.
In rising head according to the present invention, the bulk density of the rice husk ash (a) of highly crystalline to be used typically is 200g/ and rises to 400g/ liter, and preferably 200g/ rises to 300g/ liter.
In rising head according to the present invention, the thermal conductivity of the rice husk ash (a) of highly crystalline to be used typically is 0.12W/mK to 0.13W/mK and typically is 0.39W/mK to 0.4W/mK during at 1000 ℃ at 100 ℃.
Rice husk ash (a) to be used in rising head according to the present invention has surprisingly and is typically similarly worth as the ceramic hollow ball of granular filler use about thermal conductivity and bulk density, but the hollow ball of described pottery can not unrestrictedly be provided use as mentioned hereinbefore.Therefore the filler of this routine in rising head partially or fully substitutes by rice husk ash (a), described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, as the situation in rising head according to the present invention.
According to the present invention, it is preferred in rising head according to the present invention, using the rice husk ash (a) of the highly crystalline with following feature:
-be less than 1 % by weight, be preferably less than the carbon content of 0.1 % by weight,
And/or
The granularity of-0.2mm to 2mm, preferred 0.2mm to 1.5mm,
And/or
The bulk density of-200g/l to 400g/l,
And/or
-in 100 ℃ 0.12W/mK to 0.13W/mK thermal conductivity and in 1000 ℃ the thermal conductivity of 0.39W/mK to 0.4W/mK.
Preferably these all characteristics exist simultaneously.
The fire resistance of the rice husk ash (a) of the highly crystalline that can use in rising head according to the present invention by measure determine according to the thermoscope of DIN EN933-12/13/DIN51060, described thermoscope is determined in the reference temperature of >1640 ℃.
To be used in rising head according to the present invention, the rice husk ash (a) of highly crystalline can obtain by following manner: by inciting somebody to action, with the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) the crystalline substance of silica becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica comprise total share be less than 70 % by weight (i) brilliant become the silica of modification and (ii) the rice husk ash of monoclinic feldspar in the temperature of at least 1300 ℃, preferably in the temperature of at least 1400 ℃, be heat-treated until the composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) the crystalline substance of silica becomes modification, monoclinic feldspar and (iii) amorphous silica total amount meter by (i) brilliant become the silica of modification and (ii) total share of monoclinic feldspar bring up at least 70 % by weight, preferably more than 75%.
In rising head according to the present invention the rice husk ash (a) of highly crystalline to be used for example by least 1300 ℃, preferably in the temperature of at least 1400 ℃ to so-called black, that is to say that the heat treatment of the rice husk ash that is rich in carbon obtains.The rice husk ash of black for example obtains with the product title Nermat AF of Refratechnik Casting limited company.Such rice husk ash comprises the silica of 92 % by weight to 97 % by weight and until the carbon of 5 % by weight, remaining composition is oxide and the water (as moisture and as the crystallization water) of sodium, potassium, calcium, magnesium, aluminium and iron.Being included in silica in such rice husk ash has and is less than 55 % by weight, the brilliant share that becomes modified form, that is to say at least 45 % by weight, conventionally more than 50 % by weight or even exist with unbodied silica more than the silica comprising of 55 % by weight.In such rice husk ash, the brilliant share that becomes modification and exist of the conduct of silica mainly comprises tridymite or the quartz of christobalite and small amount.The particle of such rice husk ash is because relatively high carbon content has the color of black.Due to its mechanical stability deficiency, such rice husk ash is only restrictively suitable for using in rising head as filler, and especially, such rice husk ash is not for for being preferred according to the rising head of cold-box process manufacture.
From about 1300 ℃, in the temperature that preferably at least 1400 ℃ are risen, through sintering process, described sintering process causes that grain is fixed to the rice husk ash of these black---to understanding of the i.e. assessment up to now drawing according to self research---.At this, the share existing with unbodied form that is included in the silica in rice husk ash is converted into the brilliant form that becomes modification with following degree, make the composition of rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, and (iii) the remaining share of amorphous silica to account for share in the total amount of the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction of rice husk ash be 30 % by weight or still less.Meanwhile, the carbon comprising is further oxidized, to such an extent as to first the color of the original black of rice husk ash transfers grey to and finally transfer peach tone to.
In the time of the thermal sintering behavior of the rice husk ash by means of heating microscope research black, observe, sintering in the temperature of described rice husk ash between 1400 ℃ and 1600 ℃, in the temperature of 1720 ℃, reach hemisphere point, and flow point >1738 ℃.By sintering process, the rice husk ash of original black presents stable particle shape shape, to such an extent as to has improved the mechanical strength of particle.The fixed raising along with heat treated temperature realizing by sintering process improves.Best sintering temperature interval is 1400 ℃ to 1500 ℃, because in this temperature range, the sintering of rice husk ash does not still cause to each other fixed of particle.Realize the foundation that peach colourity can be considered as the integrality of sintering process.Therefore the rice husk ash of black preferably at least 1300 ℃, be preferably at least heat-treated to rice husk ash in the temperature between 1400 ℃ and 1500 ℃ and presented peach tone.
According to the present invention, thermal sintering behavior to the rice husk ash (a) of studying highly crystalline to be used is studied, and described rice husk ash obtains by the heat treatment of carrying out in temperature at least 1300 ℃, preferred at least 1400 ℃ as described in the foregoing.Determine at this, according to of the present invention to be used, at least 1300 ℃, preferably in the temperature of at least 1400 ℃ rice husk ash (a) heat treated, highly crystalline with not at least 1300 ℃, preferably compared with heat treated rice husk ash, there is higher sintering initial temperature in the temperature of at least 1400 ℃.In the time that the raw material (Nermat AF) of rice husk ash to be used in rising head according to the present invention starts sintering in 1400 ℃, at least 1300 ℃, preferably in the temperature of at least 1400 ℃ heat treated rice husk ash to have sintering under 1550 ℃ or higher temperature initial.Think at present, unbodied silica is changed into the brilliant form that becomes modification in the mode of carrying out in sintering and promoted the fixed of rice husk ash, to such an extent as to reach for use needed stability of material in rising head.
Rising head according to the present invention comprises the adhesive (b) of sclerosis.The adhesive (b) of sclerosis is interpreted as to the hardened product of adhesive or adhesive composition, wherein can use all adhesives that use in order to manufacture rising head and adhesive composition, for example thermosetting plastics constituent, starch or silicate constituent, for example waterglass.The amount of the adhesive (b) of sclerosis is arranged in the scope of 4 % by weight to 35 % by weight in the gross mass of the composition that can be shaped.
Preferably carry out the manufacture according to rising head of the present invention with cold-box method.Preferably use second-component system as adhesive composition at this, described second-component system comprises that the phenolic resins that comprises hydroxyl (OH-group) freely and PIC are as reaction counter pair.By carrying out gas treatment by means of tertiary amine, this adhesive composition is hardened to polyurethane.Therefore the adhesive of sclerosis is the hardened product of second-component system, and described second-component system comprises that the phenolic resins that comprises hydroxyl freely and PIC are as reaction counter pair.In this adhesive composition, preferably use specific fatty acid methyl ester as solvent, as its described in the European patent application EP 0804980A1; It is favourable in the situation that of fatty acid methyl ester, also using rapeseed methylester.But for the manufacture of the adhesive and the solvent that are not limited to according to the application of the cold-box method of rising head of the present invention described in the EP0804980A1, other the adhesive composition that is suitable for cold-box method and method and technology can draw from European patent application EP 0888199B1 and EP0913215B1.The disclosure of the european publishing thing of mentioning is incorporated to herein by reference.Here the composition of corresponding disclosed rising head by part or fully replace one or more fillers of mentioning there by the rice husk ash (a) of highly crystalline and become according to composition of the present invention.
According to rising head of the present invention in some cases except described highly crystalline hereinbefore, take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably become the silica of modification and (ii) the rice husk ash of monoclinic feldspar (a), also comprise other filler (d) more than the (i) brilliant of 75 % by weight.For example, according to rising head of the present invention, except the composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably become the silica of modification and (ii) outside the rice husk ash of monoclinic feldspar (a) more than the (i) brilliant of 75 % by weight, also comprise the hollow ball (d) (as described hereinbefore) using usually used as light filler, that is to say compared with conventional rising head, hollow ball (d) only partly passes through the rice husk ash of described highly crystalline (a) hereinbefore and substitutes.If rising head according to the present invention comprises the filler (d) of hollow ball as other, so in the gross mass of the composition that can be shaped, the rice husk ash (a) of highly crystalline and the total amount of hollow ball (d) are arranged in 5 % by weight to 90 % by weight, the preferred scope of 5 % by weight to 25 % by weight, and wherein the rice husk ash of highly crystalline (a) is at least 0.1 with respect to the weight ratio of hollow ball (d).But especially preferably only use the rice husk ash of highly crystalline according to the present invention.
Other filler (d) is selected from kaolin, husky, quartz sand, fire clay sand and/or coke sand and meticulous distribution, the metal oxide of inertia, as titanium, the oxide of aluminium or silicon and the like this rice husk ash of type, the composition of described rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming that is less than 70 % by weight.That is to say, the share that (iii) amorphous silica accounts for the total amount of the husk ash composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction is greater than 30 % by weight, is even greater than if desired 40 % by weight.This class rice husk ash for example obtains with the product title Nermat AF of Refratechnik Casting limited company.If manufacture rising head according to slurry process, so for example the rice husk ash of the black that is rich in carbon of the Nermat AF of the type of mentioning is suitable as filler hereinbefore.But the existence of such rice husk ash is not for the manufacture of according to being preferred in the cold-box process of rising head of the present invention.If the rice husk ash that rising head according to the present invention comprises the filler (d) as other, the amount of these rice husk ashes (d) is counted 10 % by weight at the most with the composition that can be shaped of rising head so, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as being less than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 70 % by weight.
In rising head according to the present invention, exist fibrous material (c) normally favourable, because fiber causes the additional reinforcing of rising head.Preferably use organic fibrous material, and should abandon using inorganic fibrous material.Abandon inorganic fibrous material and allow to manufacture more without doubt according to rising head of the present invention in health, because can end the particle of the sucked lung that comes from inorganic fiber.Preferably in rising head according to the present invention, use cellulose fibre, because this cellulose fibre is characterised in that the weight that it is lower.The fibre length of the cellulose fibre preferably, using at this in the scope of 30 μ m to 800 μ m.
The composition that can be shaped for the manufacture of the rising head for foundry industry according to the present invention comprises: (a) rice husk ash of highly crystalline, the composition of described rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, wherein in the gross mass of the composition that can be shaped, the amount of the rice husk ash of described highly crystalline is in 5 % by weight to 50 % by weight, preferably in the scope of 5 % by weight to 25 % by weight, (b) adhesive, (c) optional fibrous material, (d) one or more other filler if desired, and (e) (for the rising head of heat release) optionally at least one metal that can be oxidized (as aluminium, magnesium or silicon) and oxidant for the metal that can be oxidized.
About rice husk ash (a) and the manufacture of preferred adhesive (b), fibrous material (c) and other packing material (d) and other characteristic and the feature that will use for the composition that can be shaped according to the present invention, with reference to above-mentioned embodiment.Also can use adhesive composition as adhesive (b).
If the composition that can be shaped according to the present invention comprises the filler (d) of hollow ball as other, the rice husk ash of (a) highly crystalline and (d) total amount of hollow ball is in the gross mass of the composition that can be shaped in 5 % by weight to 90 % by weight, preferably in the scope of 5 % by weight to 25 % by weight so, wherein the rice husk ash of (a) highly crystalline is at least 0.1 with respect to the weight ratio of (d) hollow ball.But especially preferably only use the rice husk ash (a) of highly crystalline according to the present invention.
If the composition that can be shaped according to the present invention comprises the filler (d) of rice husk ash as other, the amount of these rice husk ashes (d) is at most 10 % by weight in the gross mass of the composition that can be shaped so, in described rice husk ash, the silica comprising that is less than 70% share exists with the form of crystalline substance change modification.
Comprise the steps according to the method for the composition for the manufacture of being shaped of the present invention, described can be shaped composition for the manufacture of the rising head for foundry industry,
-rice husk ash (a) of highly crystalline is provided, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight
-by the rice husk ash of provided highly crystalline (a) and (b) adhesive, (c) selectable fibrous material and (d) if desired one or more other filler and (e) metal that selectable (for the manufacture of the rising head of heat release) can be oxidized (as aluminium, magnesium or silicon) and mix for the oxidant of the metal that can be oxidized, to such an extent as to the amount of rice husk ash (a) accounts for the composition that can be shaped as 5 % by weight to 50 % by weight take the gross mass of the composition that can be shaped, preferably in the scope of 5 % by weight to 25 % by weight, the composition of wherein said rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight.
The rice husk ash (a) that is suitable for manufacturing according to the composition that can be shaped of the present invention can obtain in the following way: i.e. the composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica comprise total share be less than 70 % by weight (i) brilliant become the silica of modification and (ii) the rice husk ash of monoclinic feldspar be heat-treated with the temperature of at least 1300 ℃ until by the silica of (i) brilliant change modification and (ii) total share of monoclinic feldspar composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica bring up at least 70 % by weight, preferably more than 75%.Preferably in the temperature between 1400 ℃ and 1500 ℃, heat-treat.
The carbon content of rice husk ash was until 5 % by weight before heat treatment.During heating treatment, the carbon comprising is oxidized as much as possible, to such an extent as to first the color of the original black of rice husk ash transfers the tone of grey to and finally transfer peach tone to.The realization of peach colourity can consider to be used as the foundation of heat treated integrality conventionally, that is to say, reaches the foundation of the share of the desired crystalline substance change modification that accounts for the silica being included in rice husk ash.Therefore rice husk ash is preferably at least heat-treated to rice husk ash and has presented peach tone.
In order to manufacture according to rising head of the present invention, the composition that can be shaped according to the present invention is configured as rising head and the rising head of described shaping is hardened.The process being shaped preferably realizes according to slurry process (slurry filtration method), green station method (Gr ü nstandverfahren) or cold-box process or hot box process at this, wherein especially preferably uses described cold-box process.
The specific embodiment
Example 1
In the first test, the rice husk ash of Nermat AF type (Refratechnik Casting limited company) is heat-treated in high temperature furnace with 1600 ℃.Heat rate is 6K/min, and the retention time in maximum temperature is 10 minutes.The rice husk ash of original black shows peach tone subsequently.By before heat treatment and afterwards rice husk ash being carried out quantitative facies analysis and is determined by means of X-ray diffraction the following share (table 1) of unbodied silica, cristobalite, quartz and tridymite:
Table 1
By heat treatment, the share that unbodied silica accounts for the total amount of the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction of rice husk ash drops to and is less than 25 % by weight, and (i) the share of the brilliant silica (cristobalite is into main) that becomes modification rises to and exceedes 75 % by weight.
Example 2
The sintering test of other carrying out by means of the rice husk ash of Nermat AF type (Refratechnik Casting limited company) is carried out in the continuous tunnel furnace with different maximum heating temperature (1400 ℃, 1480 ℃ and 1550 ℃).In each temperature, obtain the product of pink tone.Determine (iii) unbodied silica, the (i) brilliant silica (cristobalite, quartz, tridymite) of modification and the (ii) following share (table 2) of monoclinic feldspar of becoming by before heat treatment and afterwards rice husk ash being carried out to quantitative facies analysis by means of X-ray diffraction:
Table 2
Irrelevant with maximum heating temperature, under any circumstance all carry out unbodied silica (iii) change into as much as possible the silica of (i) brilliant change modification and change into if desired as the (ii) silica of the composition of monoclinic feldspar, to such an extent as to after heat treatment, the share that the silica existing with unbodied form accounts for the total amount of the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction of rice husk ash is less than respectively 10 % by weight.
Example 3
Two kinds of samples of the rice husk ash to pink tone and studying in the composition aspect of mineral with two kinds of samples of the commercially available rice husk ash of the product title Nermat AF of Refratechnik Casting limited company.Result following (table 3):
Table 3
The composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount of unbodied silica there is the share (sample 1) of the unbodied silica that is less than 17 % by weight or be even less than the share (sample 2) of 15 % by weight, and the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction that exceedes 80 % by weight or exceed the share of 85 % by weight of rice husk ash becomes the silica of modification and (ii) monoclinic feldspar formation by (i) brilliant.Deviation in the composition of the mineral of the rice husk ash of these two kinds of sample Nermat AF or pink tone is owing to belonging to different batches.The raw material of rice husk ash is inevitably subject to certain quality fluctuation as natural product.
Example 4:
The rice husk ash of Nermat AF type (Refratechnik Casting limited company) is heat-treated in high temperature furnace with 1400 ℃.Before heat treatment and afterwards, determine the chemical composition of rice husk ash by means of x-ray fluorescence analysis.Result following (table 4):
Table 4:
Carbon share obviously reduces due to sintering process.
In chemical analysis the total content of definite silica by unbodied silica, brilliant become the silica (cristobalite, tridymite and quartz) of modification and form as the silica of the composition of monoclinic feldspar if desired.
Example 5: manufacture and the application of emitting lid
Two kinds of compositions that can be shaped according to the present invention are used to manufacture and emit lid.The first is adiabatic material according to the composition that can be shaped of the present invention (example 5a, table 5a), and the second is the riser heating material of heat release according to the composition that can be shaped of the present invention (example 5b, table 5b).
For relatively, emit lid to be manufactured by the riser heating material of the adiabatic material of commonly using or conventional heat release.
Table 5(example 5a, the heavy component of GT=meter):
Table 5b(example 5b, the heavy component of GT=meter):
Emit the manufacture of lid independently to comprise the steps: with the composition that can be shaped using
The composition of the solid of-composition that mixing energy is shaped equably,
-interpolation adhesive,
-be shaped and emit lid,
Lid is emitted in-sclerosis.
The composition that can be shaped according to the present invention using of example 5a and 5b is proved to be to be suitable for manufacturing and emits lid.Definite in foundry trial, although comprise according to according to the present invention can be shaped composition emit lid lower about the content of its cooling performance aspect hollow ball, with the rising head material by conventional form emit lid and almost as broad as long.This for example illustrates and comes from routine 5b(Fig. 1) the composition that can be shaped that comprises conventional heating emit lid and comprising according to the comparison of the cooling curve that emits lid of the composition that can be shaped of heat release of the present invention.
Claims (15)
1. the rising head for using at foundry industry, comprising:
(a) rice husk ash, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight;
(b) adhesive of sclerosis;
(c) optional fibrous material;
(d) one or more other filler if desired;
(e) the optional metal that can be oxidized and the oxidant for the described metal that can be oxidized.
2. according to the rising head described in the next item up claim, it is characterized in that, what be included in silica in described rice husk ash (a) becomes the share of the silica that share that the form of modification exists comprises one or more brilliant change modifications that come from group be made up of cristobalite, tridymite, quartz with crystalline substance.
3. according to the rising head described in any one in the claims, it is characterized in that,
The carbon content of-described rice husk ash (a) is less than 1 % by weight, is preferably less than 0.1 % by weight,
And/or
The granularity of-described rice husk ash (a) is 0.2mm to 2mm, preferably 0.2mm to 1.5mm,
And/or
The bulk density of-described rice husk ash (a) is 200g/l to 400g/ liter,
And/or
The thermal conductivity of-described rice husk ash (a) is generally 0.12W/mK to 0.13W/mK and in the time of 1000 ℃, is generally 0.39W/mK to 0.4W/mK in the time of 100 ℃.
4. according to the rising head described in any one in the claims, it is characterized in that, the adhesive (b) of described sclerosis is the hardened product of second-component system, and described second-component system comprises that the phenolic resins that comprises hydroxyl freely and PIC are as reaction counter pair.
5. according to the rising head described in any one in the claims, it is characterized in that, the hollow ball that comprises the filler (d) as other,
Wherein in the gross mass of the composition that can be shaped of described rising head,
(a) rice husk ash, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than 75% the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming, and
(d) hollow ball,
Total amount be arranged in 5 % by weight to 90 % by weight, the preferably scope of 5 % by weight to 25 % by weight, and described rice husk ash (a) is at least 0.1 with respect to the weight ratio of described hollow ball (d).
6. according to the rising head described in any one in the claims, it is characterized in that, the rice husk ash that comprises the filler (d) as other, the composition of described rice husk ash ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming that is less than 70 % by weight, and the amount of described rice husk ash (d) is at most 10 % by weight in the gross mass of the composition that can be shaped of described rising head.
7. for the manufacture of the composition that can be shaped of the rising head for foundry industry, comprising:
(a) rice husk ash, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight;
(b) adhesive;
(c) optional fibrous material;
(d) one or more other filler if desired;
(e) optional at least one metal that can be oxidized and for the described oxidant of metal that can oxidation.
8. the composition that can be shaped according to claim 7, is characterized in that, described adhesive (b) is second-component system, and described second-component system comprises that the phenolic resins that comprises hydroxyl (OH-group) freely and PIC are as reaction counter pair.
9. according to the composition that can be shaped described in claim 7 or 8, it is characterized in that,
Comprise the filler (d) of hollow ball as other,
The gross mass of the composition being wherein shaped in described energy,
(a) rice husk ash, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight, and
(d) hollow ball,
Total amount be arranged in 5 % by weight to 90 % by weight, the preferably scope of 5 % by weight to 25 % by weight, and described rice husk ash (a) is at least 0.1 with respect to the weight ratio of described hollow ball (d).
10. according to the composition that can be shaped described in any one in claim 7 to 9, it is characterized in that, the rice husk ash that comprises the filler (d) as other, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as being less than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 70 % by weight
And the amount of described rice husk ash (d) is at most 10 % by weight in the described gross mass of composition that can be shaped, the form that the share that is less than 70% silica comprising in described rice husk ash becomes modification with crystalline substance exists.
11. 1 kinds of methods for the manufacture of the composition that can be shaped, the described composition that can be shaped is for the manufacture of the rising head for the manufacture of industry, and described method comprises the steps:
-rice husk ash (a) is provided, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight
-by provided described rice husk ash (a) with
(b) adhesive,
(c) selectable fibrous material and
(d) one or more other filler if desired
(e) the selectable metal that can be oxidized and the oxidant mixing for the described metal that can be oxidized,
To such an extent as to the amount of described rice husk ash (a) is in the gross mass of the described composition that can be shaped, in the described composition that can be shaped, be positioned at 5 % by weight to 50 % by weight, preferably in the scope of 5 % by weight to 25 % by weight, the composition of described rice husk ash can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica to comprise total share be at least 70 % by weight, preferably more than the (i) brilliant silica of modification and the (ii) monoclinic feldspar of becoming of 75 % by weight.
12. methods according to claim 11, it is characterized in that, by the composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) the total amount meter of amorphous silica comprise total share be less than 70 % by weight (i) brilliant become the silica of modification and (ii) the rice husk ash of monoclinic feldspar in the situation that of at least 1300 ℃ of temperature heat treatment until by the silica of (i) brilliant change modification and (ii) total share of monoclinic feldspar composition can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, the i.e. (i) brilliant silica that becomes modification, monoclinic feldspar and (iii) amorphous silica total amount meter and bring up at least 70 % by weight, preferably more than 75%.
13. according to the method described in any one in claim 11 and 12, it is characterized in that, described heat treatment is carried out between the temperature of 1400 ℃ and 1500 ℃.
14. according to claim 11 to the method described in any one in 13, it is characterized in that, by described rice husk ash at least heat treatment until described rice husk ash presents peach tone.
15. 1 kinds of rice husk ashes (a) are as the application of the light filler for the manufacture of the composition that can be shaped of the rising head for foundry industry, described rice husk ash take the composition that can detect by the quantitative facies analysis of carrying out by means of X-ray diffraction in described rice husk ash, (i) brilliant become the silica of modification, (ii) monoclinic feldspar and (iii) the total amount of amorphous silica comprise total share as at least 70 % by weight, preferably more than the silica of 75% (i) crystalline substance change modification and (ii) monoclinic feldspar.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011079692A DE102011079692A1 (en) | 2011-07-22 | 2011-07-22 | Feeders and moldable compositions for their preparation |
| DE102011079692.4 | 2011-07-22 | ||
| PCT/EP2012/064378 WO2013014118A2 (en) | 2011-07-22 | 2012-07-23 | Feeder and shapeable composition for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103813869A true CN103813869A (en) | 2014-05-21 |
| CN103813869B CN103813869B (en) | 2016-10-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280045885.6A Active CN103813869B (en) | 2011-07-22 | 2012-07-23 | Rising head and the compositions that can shape manufactured for it |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US9868149B2 (en) |
| EP (1) | EP2734321B1 (en) |
| CN (1) | CN103813869B (en) |
| BR (1) | BR112014001493B1 (en) |
| CA (1) | CA2842515A1 (en) |
| DE (1) | DE102011079692A1 (en) |
| EA (1) | EA027797B1 (en) |
| PL (1) | PL2734321T3 (en) |
| TW (1) | TW201317197A (en) |
| WO (1) | WO2013014118A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114535496A (en) * | 2016-06-30 | 2022-05-27 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Core-shell particles for use as a filler for riser materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013150159A2 (en) * | 2012-08-03 | 2013-10-10 | Chemex Gmbh | Mouldable exothermal compositions and feeder thereof |
| US9678269B2 (en) | 2014-05-16 | 2017-06-13 | Corning Incorporated | Multimode optical fiber transmission system including single mode fiber |
| DE102015120866A1 (en) * | 2015-12-01 | 2017-06-01 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Process for producing refractory composite particles and feeder elements for the foundry industry, corresponding feeder elements and uses |
| DE102016205960A1 (en) | 2016-04-08 | 2017-10-12 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Use of closed-pore microballs of expanded perlite as a filler for the production of moldings for the foundry industry |
| DE102016112039B4 (en) * | 2016-06-30 | 2019-07-11 | Refratechnik Holding Gmbh | Heat-insulating plate, in particular cover plate for molten metal, and method for producing the plate and its use |
| DE102016112044B4 (en) * | 2016-06-30 | 2019-01-03 | Refratechnik Holding Gmbh | Use of a heat-insulating plate for insulating molten metal from the atmosphere or a metallurgical vessel |
| DE102017131255A1 (en) | 2017-12-22 | 2019-06-27 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | A method of making a metallic casting or a cured molding using aliphatic polymers comprising hydroxy groups |
| DE102018121769A1 (en) | 2018-09-06 | 2020-03-12 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Process for producing a metallic casting or a hardened molded part using an aliphatic binder system |
| DE102021203371A1 (en) | 2021-04-01 | 2022-10-06 | Refratechnik Holding Gmbh | Backfill for the production of a refractory, unfired shaped body, such shaped bodies, methods for their production, and lining of a kiln and kiln |
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2011
- 2011-07-22 DE DE102011079692A patent/DE102011079692A1/en not_active Withdrawn
-
2012
- 2012-07-20 TW TW101126353A patent/TW201317197A/en unknown
- 2012-07-23 WO PCT/EP2012/064378 patent/WO2013014118A2/en active Application Filing
- 2012-07-23 CN CN201280045885.6A patent/CN103813869B/en active Active
- 2012-07-23 EP EP12740127.1A patent/EP2734321B1/en active Active
- 2012-07-23 US US14/234,315 patent/US9868149B2/en active Active
- 2012-07-23 EA EA201490323A patent/EA027797B1/en not_active IP Right Cessation
- 2012-07-23 CA CA2842515A patent/CA2842515A1/en not_active Abandoned
- 2012-07-23 BR BR112014001493A patent/BR112014001493B1/en not_active IP Right Cessation
- 2012-07-23 PL PL12740127T patent/PL2734321T3/en unknown
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| GB1432707A (en) * | 1972-07-28 | 1976-04-22 | Univ California | Anhydrous amorphous siliceous material derived from organic plant material its process of preparation and compositions containing same |
| JPS5983974A (en) * | 1982-10-29 | 1984-05-15 | 松下電工株式会社 | Inorganic hardened body |
| DE3516033A1 (en) * | 1985-05-04 | 1986-11-06 | L. Bregenzer Gießereibedarf GmbH & Co, 7000 Stuttgart | Method and feeder mould for the production of a feeder sleeve, in particular a lateral feeder sleeve, having a curved feeder duct |
| CN1115978A (en) * | 1993-10-15 | 1996-01-31 | 王道集团公开有限公司 | Improvements in the production of biogenetic silica from organic plant matter |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114535496A (en) * | 2016-06-30 | 2022-05-27 | 胡坦斯·阿尔伯图斯化学厂有限公司 | Core-shell particles for use as a filler for riser materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2842515A1 (en) | 2013-01-31 |
| EA027797B1 (en) | 2017-09-29 |
| BR112014001493A2 (en) | 2017-02-14 |
| DE102011079692A1 (en) | 2013-01-24 |
| EP2734321A2 (en) | 2014-05-28 |
| PL2734321T3 (en) | 2017-04-28 |
| EP2734321B1 (en) | 2016-09-28 |
| WO2013014118A2 (en) | 2013-01-31 |
| US9868149B2 (en) | 2018-01-16 |
| CN103813869B (en) | 2016-10-19 |
| WO2013014118A3 (en) | 2013-05-30 |
| TW201317197A (en) | 2013-05-01 |
| EA201490323A1 (en) | 2014-06-30 |
| BR112014001493B1 (en) | 2018-10-09 |
| US20140235750A1 (en) | 2014-08-21 |
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